Mineral oil



Patented Jan. 28, 1941 UNITED STATES 2,230,022 PATENT OFFICE MINERAL OIL Mario S. Altamura, Henry G. Berger, and Darwin E. Badertscher, Woodbury, N. .L, assignors to Socony-Vacuum Oil Company, Incorporated, New York, N. Y., a corporation of New York No Drawing.

Application October 26, 1939, Serial No. 301,372

15 Claims. (Cl. 252-51 the emulsive properties of oils ofthe indicated demulsibility number. Additionally, many of the oils refined by modern methods, even without such additive agents, are somewhat deficient in this respect.

The Herschel 130 F.-demulslbillty number, spoken of as D. N., and the steam emulsion number, spoken of as S. E. N. are numerical values obtained from the corresponding tests, devised to measure the resistance of the'oil to the formation of semi-permanent emulsions with water. Since practically any lubricating oil may be used under conditionswhere such emulsions may be formed, as for example due to the presence of condensed water vapor in the crankcase of an automobile. the problem of reducing the sensitivity of such oils to emulsion formation becomes one of importance.

The invention has for its object the provision of refined lubricating oils with or without additive agents which may adversely affect the emulsive properties of the oil, which oils, when produced according to this invention, are characterized by improved emulsive properties asindicated by the D. N. and the SE. N., it being remembered that improvedfemulsive properties are indicated by a raising of the D. N. and a lowering of the S. E. N.

The S. E. N. is determined according to test No. 28, A. S. T. M. (Serial D 157-36), and is obtained by passing steam into oil to form an emulsion, and observing the number of seconds required for separation of oil and water under closely specified conditions. The ability of the oil to resist emulsification is considered as inversely proportional to the S. E. N. in seconds. The demulsibility test, reported as D. N., is conducted in accordance with Federal Standard Stock Catalogue VV-L-791-a Method 320.32, F.6Z at 130? F. and comprises emulsification of oil and water mechanically at 130 F. under closely specified conditions, followed by observation of the rate of settling and reported as a numerical value, higher values denoting more acceptable oils.

The two tests are not comparable, since frequently an oil which is quite acceptable accordclass may be substantially improved with respect to both tests by the addition thereto of small amounts of amine oxides such as those obtained by the reaction of tertiary amines and hydrogen peroxides together with small amounts of blown fatty oils such as blown lard oil.

As an example of one of the members of the class of amine oxides which may be used. there may be mentioned triamylamine oxide. Triamyl' amine oxide may be prepared according to the method of Dunstan and Gouldlng (Journal of the Chemical Society (London) 75, 10044 (1899)) which was concerned with the preparation of oxides of lower amines. Minor changes were necessary for the preparation of the higher oxide.

The preparation follows essentially the equation (C5Hii)3N+H2O2= (C5H11)3NO+H2O, and, in brief, may be effected as follows: Twenty-five grams of triamylamine (commercial mixed isomers) is placed in a flask equipped with thermometer, stirrer, and reflux condenser. The amine is dissolved in 850 ml. of grain alcohol, and ml. of 3% hydrogen peroxide is added.- The mixture is held at 60-65 C. for about 26 hours. Then it is distilled under partial vacuum to remove most of the alcohol, whereby a residue of two layers remains. If the pure product is desired, the top layer of unreacted amine is removed, and the lower aqueous layer is extracted with ether. The remaining aqueous layer is then concentratedon a steam bath, and the moist, viscous residue of oxide is further dried in a vacuum desiccator over anhydrous calcium chloride. Should the reaction product mixture. be desired, the residue from alcohol distillation is directly concentrated on the steam bath, whereby the two layers coalesce into a viscous homogeneous liquid which may be further dried in a vacuum desiccator. In order to reduce the volume of the reaction medium and insure a higher percentage of the amine oxide in the reaction product it is desirable to use Superoxol (which is 30% hydrogen peroxide) in thereaction. For the same quantity of amine 12 ml. Superoxol" and only ml. alcohol are required.

Since it has been found that the class of amine oxides generally are useful for this purpose, the triamylamine oxide above mentioned may be taken as exemplary of that class of amine oxides designated by the formula (RR'R")NO wherein R, R, R" may be alkyl, aryl, alkaryl or aralkyl groups, such as for example, triamylamine just mentioned. N-diamylaniline, N, N, N, N'-Tetraethyltrimethylenediamine, ethyldicyclohexylamine and other amines may be subjected to an oxidation. procedure, similar to that outlined above, to produce amine oxides useful for the purposes of this invention.

the D. N. or Herschel demulsibility of an oil and consequently this invention is in part rected to the use in oils of amine oxide mate alone for that purpose.

It will be remembered inrthesdescription preparation of triamylamine and t t cedure could be conducted t v relatively pure oxide by way oi -plies separation followed by ether extraction qr a reaction product mixture which was produced by concentration without phase separation and ether extrac-,

tion. These products both have about the same acti or .,.thqpurposes oi ti 1is invention and v d v is connection the a tertiary amine and J beheld toindicate genernipound and the reaction oxide of an organic tertiary amine or the s cific name of the oxide such as triamyla ine oxide" will be held to refer specifi to purified product. The terms amine 7 ion mixture or the reaction mixture ifically'designated with a compound name as,.;. fo'r example, "triamylamine oxide reaction mixture will be held to refer specifically to the i pure fproduct.

Blownjatty oils such as blown castor oil, blown rapeseed oihblown lard oil, and similar products arelusedr in combination in most cases with the amine oxide' 'products. These oxidized materials or which-blown lard oil is an example, have been used as emulsion breakers in connection with oil field emulsions. When added to refined oils, they are capable of improving only the S. E. N. of the oil. andt-hatto 39. varying degree. Various mixtures of the two elements disclosed herein, namely, amine oxides and the blown fattyoils may be used for the major purpose of this invention. In general, desirable improvement of oils may be effected by the addition thereto of from about 0.001% by weight to about 1.0% by weight of total corrective additives of which from about 10% to about by weight will be the amine oxide element, the remainder being the blown fatty oil. A convenient way of adding these reagents happens to be that of making a mixture consisting of about one-third of the amine oxide material and two-thirds of the blown fatty oil. For example, a mixture may be used which consists of about 28% 01 triamylamine oxide reaction product and about 72% of blown lard 'oil.

To demonstrate the effectiveness 01' these reagents, certain tests were made, using as a base stock n S. A. E. 20 lubricating oil, to which, in i's ta nt:"e's, 0.1% and in other cases 0.5%

by weiglit bf a commercial pour depressant having adverse effect on emulsive properties was added. The results of the tests are set forth in iollowing tabulation:

TABLE I Concvmration of l r corrective i material i y flr-zs-r Sam-LE 1 I Group I i 1 (l) S. A E. 20oil-plain..... None l 230 2) s. A. .+o.1% depressant. 1 Nnntg flg I} 300+ a s. A. E.+0.5% depressant None 1.1m 400+ Group II S. A. E. 20 oil+0.l% )ur depressant, to which has .cn z f l l d 4 riamy amine oxi e *0. 025' Blown lard oil 0.051 (5) Triamylamine oxide rcaction mixture.. 0033 N2" Blown lard oil 0. 050

Tsar Sx'nrn (6) Triamylamine oxide-blown lard oil mixture 0. 085 1020 90 (7) Triamylamine oxide reaction mixture-blown lard oil mixture... 0. 000 1020 Group III 7 S. A. E. 20 oil-+05% ur depressant, to which has en ad)de!( l: 1 d (8 riamy amine oxi 0. 025 Blown lard oil U. 047 mm (9) Triamylamine oxide rcac- 1 tion mixture 0. 038 W) Blown lard o1] um? It will ,be observed that both the D. N. and S. E. N. are in all cases considerably improved. In items 4, 5, 8, 9, the triamylamine oxide or reaction mixture (as the case might be) and the blown lard oil were added separately to the oil. In items 6 and 7; the mixture of triamylamine oxide and blown lard oil for item 6, and triamylamine oxide reaction mixture and blown lard oil for 7, were made up externally, to proportions set forth above, and the resulting mixture was added to the oil.

Further test with other materials of the general class of amine oxides are shown in Table II.

TABL! II rem using base stock (.9. A. E. 20 plus 0.1 of an additive having adverse properties tCancer!f Base stock Improved oil ra ion 0 Corrective material tested comm materials D. N. S.E.N. D. N. S. E. N.

. (1) N N, Nf, P-tetraethyltrirnethylenedlamine dioxide reacion mix ure. 0.037 gr no a olilli d i i. 0.040 325 amy an no oxi e react on mixture 0. 008 gi lard o u u 0.024 127 3 myan o0 ereactionm uro 0.022 (4 BP "5 t ina ait-ii" m no m0 amy an: ne 0 a row on uro 0.021 (5) glolwlnilardloguulnnifiuafl -2 0.050 127 310 1260 108 t y icyco ex am e doreactonmixture 0.043 Blown lard oil? 0. 025 w 305 (6) Etbyldlcyclohexyiamine oxide reaction mixture 0. 02% w 305 16 m Et ti l ilig l 1 inc id reacti mixt 3% m 1 y c o 0 am ox 0 on are Blown lard 011:? 0. 047 W 305 2separations and 125.

Some reference has previously been made herein to the concentration in which these corrective materials may be used. This will be reviewed now referring to triamylamine oxide as representative of the group.

In general, desirable improvement in oils may be effected by the addition thereto of from about 0.001 percent by weight to about 1.0 percent by weight of the corrective mixture, in which corrective mixture the triamylamine oxide portion will range from about 10 percent to about percent by weight of the total corrective mixture. The preferred amounts to be used may be expressed as from about 0.05 percent to about 0.1 percent by weight of the corrective mixture, in which mixture the triamylamine oxide portion will be from about 25.percent to about 30 percent by weight. It is of course to be understood that the two ingredients may be added to the oil separately, or may be admixed prior to addition to the oil.

Also, since the triamylamine oxide element has valuable properties alone for improving the D. N. or Herschel demulsibility, this invention is in part directed to the use in oil of that product. When used alone, it may be used in proportions of from about 0.01 to about 0.1 percent by weight.

In the claims and in this specification we have been speaking of improving the emulsive properties of oils and of oils having improved emulsive properties. It must be remembered that these terms specifically refer to those changes in the emulsive properties which are indicated by increases in the D. N. or Herschel demulsibility number and by decreases in the S. E. N. or steam emulsion number.

We claim:

1. A lubricating oil of improved emulsive properties comprising a refined mineral oil to which has been added a small amount of the reaction product of a tertiary organic amine and hydrogen peroxide.

2. A lubricating oil of improved emulsive properties comprising a refined mineral oil to which has been added a small amount of the oxide of an organic tertiary amine.

3. A lubricating oil of improved emulsive properties comprising a refined mineral oil to which has been added a small amount of amine oxide reaction mixture derived from reaction of an organic tertiary amine and hydrogen peroxide.

4. A lubricating oil of improved emulsive properties comprising a refined mineral oil to which has been added a small amount of the reaction product produced by reacting hydrogen peroxide with a tertiary amine at least one of the substituents in which is an alkyl.

5. A lubricating oil of improved emulsive properties as measured by both S. E. N. and D. N. consisting of a refined mineral oil to which has been added a small amount of the reaction product of a tertiary amine and hydrogen peroxide and a small amount of a blown fatty oil.

6. A lubricating oil of improved emulslve p perties comprising a refined mineral oil to which has been added a small amount of the reaction product of triamylamine and hydrogen peroxide.

7. A lubricating oil of improved emulsive properties comprising a refined mineral oil to which has been added a small amount of triamylamine oxide.

8. A lubricating oil of improved emulsive prop,- erties comprising a refined mineral oil to which has been added a small amount of triamylamine oxide reaction mixture.

9. A lubricating oil of improved emulsive properties comprising a refined mineral oil to which has been added from about 0.01 .to about 0.1 weight percent of the reaction product of triamylamine and hydrogen peroxide.

10. A lubricating oil of improved emulsive prop erties as measured by both S. E. N. and D. N. consisting of a refined mineral oil to which has been added a small amount of the reaction product of triamylamine and hydrogen peroxide and a small amount of blown lard oil.

11. A lubricating oil of improved emulsive properties as measured by both S. E. N. and D. N. consisting of a refined mineral oil to which has been added a small amount of triamylamine oxide and a small amount of blown lard oil.

12. A lubricating oil ofimproved emulsive properties as measured by both S. E. N. and D. N. consisting of a refined mineral oil to which has been added a small amount of triamylamine oxide reafltion mixture and a small amount of blown lard o 13. A lubricating oil of improved emulsive properties as measured by both S. E. N. and D. N. consisting of a refined mineral oil to which has been added from about 0.0001 to about 0.9 weight percent of the reaction product of triamylamine and hydrogen peroxide and from about 0.9 to about 0.0001 weight percent of blown lard oil.

14. A lubricating oil of improved emulsive properties as measured by both S. E. N. and D. N. consisting of a refined mineral oil to which has been added from about 0.0001 to about 0.9 weight percent of triamylamine oxide and from about 0.9 to about 0.0001 weight percent of blown lard oil.

15. A lubricatingoil of improved emulsive properties as measured by both S. E. N. and D. N. consisting of a refined mineral oil to which has been added from about 0.0001 to about 0.9 weight percent of triamylamine oxide reaction mixture and 5 from about 0.9 to about 0.0001 weight percent of blown lard oil.

MARIO S. ALTAMURA. HENRY G. BERGER. DARWIN E. BADERTSCHER. 

